Surface treated inorganic solid polymerization catalyst and method of polymerization therewith



3,166,542 SURFACE TREATED INORGANIC sour) POLYM- ERIZATION CATALYST ANDMETHUD OF Pfi LYMERIZATION THEREWITH Adam ()rze'chowski, Brookline, andJames C. MacKenzie, Wellesley Hills, Mass, assignors to CabotCorporation, Boston, Mass, a corporation of Deiaware No Drawing.Original application Apr. 11, 1960, Ser. No. 21,110. Divided and thisapplication Feb. 3, 1961,

Ser. No. 86,868

. 25 Claims. (Cl. 26093.7)

. This invention relates to the polymerization and copolymerization ofmonoolefins and diolefins such as ethylene, propylene, butene-l,styrene, isoprene and butadiene and includes within its scope improvedcatalysts for such polymerization reactions.

This application is a division of US. patent application, Serial No.21,110, filed on April 11, 1960, which application was in turn'acontinuation-in-part of US. patent application Serial No. 2,861, filedJanuary 18, 1960, now abandoned.

Accordingly, it is a principal object of the present invention toprovide a novel process for polymerizing monoand diolefins and mixturesthereof.

Other objects of the present invention will in part be obvious and willin part appear hereinafter.

In accordance with the presentinvention, monoand diolefins, preferablythose containing not over 8 carbon atoms, are polymerized orcopolymerizcd by catalysts comprising (a) the product of the reactioncarried out under certain conditions between a halide-type compound of agroup IVa, Va or VIa metal and a finely divided particulate inorganicsolid having surface hydroxyl groups thereon, and (b) an organometalliccompound. The polymerization or copolymerization reaction can beeffected at suitable temperatures within the range of from about 25 C.to about 250 C., and pressures ranging from below atmospheric upwardlyto any desired maximum pressure, for example, 30,000 p.s.i.g. or evenhigher pressures.

Inorganicsolids suitable for the purposes of the present inventiongenerally includeany inorganic compound which is available in finelydividedparticulate form with hydroxyl groups on the surface thereof. Forexample, oxides such as alumina, titania, zirconia, silica, thoria andmagnesia, silicates such as chrysotile, actinolite and crocidolite, andaluminates such as corundum and bauxite are all generally suitable forthe purposesof the present invention.

Halide-type'compounds of group IVa, Va and -Vla metals (hereinaftergenerally referred to as transition metal halides) suitable for thepurposes of the present invention are the compounds conforming to thegeneral empirical formula:

TO X

wherein T is a metal of groups No, Va or VIa (where the group numberscorrespond to the Mendeleev Periodic System), is oxygen, a equals 0, 1or 2, each X is a halogen, and b is an integer from 1 to 6.

Examples of suitable compounds conforming to the general formula arehalides of group No, Va and VIa metals such as titanium tetrachloride,zirconium tetrachloride, vanadium tetrachloride, chromium trichloride,tungsten hexachloride and titanium tetraiodide, and oxyhalides of groupIVa, Va and VIa metals, such as vanadium oxychloride.

3,166,542 Patented Jan. 19, 1965 The conditions under which reactionbetween the transition metal halide and the finely divided inorganicsolid can be accomplished are subject to considerable variation.

However, in order to obtain a catalyst component with exceptionally highactivity and reproducible character and performance, three relativelysimple refinements have been found to be all important, namely (1) thefinely divided inorganic solid should be essentially dry and anhydrous(i.e. free of molecular water in any form) at the time it is broughtinto contact with the transition metal halide, (2) special provisionshould be made to withdraw gaseous by-products of the reaction (forexample, HCl) from the reaction mixture and (3) the reaction between thefinely divided inorganic solid and the transition metal halide mustoccur at temperatures below about C.

Generally, the said reaction can be carried out by contacting saidinorganic solid with said transition metal halide,

preferably in a solution thereof in an inert hydrocarbon medium, andmaintaining the two reactants in intimate contact for a period of timesufiicient to eifect the desired chemical reaction resulting in thechemical bonding of the transition metal to the inorganic solid. Thelength of time required to effect a given amount of such reaction andchemical bonding is largely dependent upon the .tem-

perature of the reaction mixture and the rate of removal of the gaseousby-products. Generally speaking, any

temperature between about 0 C. and 105 C. can be used satisfactorily,but room temperature or higher will generally be used. Assumingprovision ismade for intimate contact of the dry inorganic solid and thetransition metal halide and for active Withdrawal of gaseous byproducts,such as HCl, the time required to accomplish the chemical reactionneeded will vary from periods of the order of hours (i.e. from about 0.5hours to'about 20 hours) at room temperature to periods of the order ofminutes (i.e. from about 0.5 to about 20 minutes) at temperatures ofabout 105 C. Temperatures substantially higher than about 105 C., e.g.200 C., are completely needless and therefore of little or no interest,

although as disclosed in application Serial No. 2,861, temperatures ashigh as about 300 C. or higher can be.

utilized if desired. Moreover, temperatures above about 105 C. should beavoided because the catalyst c0mpo vapors of said metal halide at atemperature of from:

about 20 C. to about 105 C. from a few minutesto about 1 hour or moredepending upon the temperature and the rate of removal of the gaseousby-products. Said vapors can be supplied under their own vaporpressureusing a partial vacuum if necessary, or with the aid of a dry inertcarrier gas such as nitrogen. This vapor phase treatment can beaccomplished in any suitable manner such as by circulating the vaporsthrough the particulate;

solid in a fixed, moving or fluidized bed reactor.

Removal of the gaseous by-products of the reaction can be accomplishedin many Ways such as (a) by accom-* plishing the reaction under vacuum,(15) sweeping the reaction vessel with an inert gas such as (dry,oxygenfree) nitrogen, (c) by carrying out the reaction at sufficientlyelevated temperatures while stirring to drive off the gaseousby-products (d) by carrying out the reaction areaesa 3 in a refiuxingsolvent and (e) by any combination of these.

The accomplishment of an actual chemical reaction of controlled extentbetween the finely divided inorganic solid and the transition metalhalide is of utmost importance in obtaining the exceptional active andefficient catalyst components described in this invention, eg the gramsof polymer producible per gram of catalyst employed is generally highlydependent upon both the amount of transition metal chemically combinedwith a given amount of the said inorganic solid and the manner in whichit is chemically combined therewith. These, in turn, are dependentlargely on two main factors, each of which is separately controllable toa large extent. The first factor in question is the molar quantity ofhydroxyl groups available on the surface of the inorganic solid perweight of said solid. For a given inorganic solid, for example, thisfirst factor is lar ely a matter of (a) the fineness of subdivision ofthe form in which said solid is available and (b) the chemical nature ofthe surface of said solid, the upper limit clearly being reached whenthe solid is ultra fine and the surface thereof is stoichiometricallysaturated with hydroxyl groups. The second factor in question is theproportion of the said surface hydroxyl groups which are actuallychemically reacted with the transition metal halide with resultant lossof HCl and formation of chemical linkages of the transition metal to thesolid and the number of such chemical linkages established with eachtransition metal atom. For a given pair of reactants, i.e.solid-i-transition metal halide, this second factor will be largelydetermined by reaction conditions and principally by the reactiontemperature used.

In view of the above discussion it is clear that in preparing thesurface reacted inorganic solids of the present invention, the smallerthe average particle size of the inorganic solid and the larger thequantity of hydroxyl groups on the surface thereof, the greater will bethe potential activity and efiiciency of the resulting catalystcomponent producible therefrom. Accordingly, it is important to use asthe star-ting material particulate finely divided inorganic solidshaving an average equivalent particle diameter of less than about 1micron and preferably less than about 0.1 micron and which have asubstantial hydroxyl group content on the surface thereof. Accordingly,pyrogenic metal or metalloid oxides, i.e. oxides produced by the vaporphase oxidation or hydrolysis of a corresponding metal compound aregreatly preferred.

In short, to reduce this discussion of extent of reaction between theinorganic solid and the transition metal halide to the simplest possibleterms, it is believed that the surface reacted inorganic solid can bestbe described and specified as;follows: Preferred for imparting optimumcatalytic activity and providing maximum catalyst efiiciencies when usedwith a given organometallic compound in a given system are thoseinorganic solids which have from between about l 1O- and about 5x10-gram atoms of the transition metal chemically attached to the surfacethereof per gram of said solid. Still quite useful and practical,however, particularly when for other reasons amounts of 1 part or moreby weight of the inorganic solid per 100 parts of the polymer productare desired, are those surface reacted inorganic solids which contain aslittle as 1 10 gram atoms of transition metal chemically combined to thesurface thereof per gram of said inorganic solid. Although the mechanismof the reaction between the transition metal compound and the inorganicsolid is not completely understood, it is known that the transitionmetal compound reacts with the hydroxyl groups on the surface of theinorganic solid liberating gaseous by-products such as HCl, which mustbe withdrawn from the reaction zone in order for the reaction to proceedto completion. It is believed, but there is no intention to be bound bythis explanation,

If the precaution of using a substantially anhydrous inorganic solidand/ or removing the gaseous by-products such as HCl, are not observed,then the desired chemical reaction, such as that suggested by the aboveillustrative equation, either does not occur at all or does notpredominate to the extent necessary to produce a superior activecatalyst component. Instead products are obtained which are veryinferior as catalyst components in that (a) enormously less polymer pergram of catalyst is produced and (1)) reaction rates for production ofpolymer are enormously lower. Apparently, if the gaseous lay-product,such as hydrogen chloride, are not removed, retardation and evenreversal of the reaction occurs either preventing the formation of thedesired product having high catalytic activity, or contaminating it withharmful or inactive components.

Equally important in obtaining the desired reaction product is the useof a dry inorganic solid in the above reaction. Therefore, if the saidsolid to be used contains molecular water in any form and/or tends toadsorb same on exposure to humid atmospheres, etc., it must be driedimmediately before use or, after drying, must be maintained continuouslyout of contact with water or water vapor until used.

Also, it is pointed out that in order to obtain a catalyst component ofthe highest possible activity, aside from observing the above importantprecautions and reaction conditions, it is also recommended that thequantity of transition metal halide with which the inorganic solid iscontacted be at least approximately sufficient to provide one atom oftransition metal for each three hydroxyl groups on the surface of theinorganic solid, in order to react all of the active hydroxyl groupspossible, since those left unreacted might otherwise deactivate aportion of the organometallic component of the catalyst which will beadded subsequently.

Moreover, it is generally necessary to use somewhat more than thisminimum amount of transition metal halide, and to restrict the reactiontemperatures to less than C. in order to favor the reactions typified byEquations 1 and 2 over those illustrated by Equations 4 and 5 whichfollow, because the products of Equations 1 and 2 are much more activeas catalyst components than products such as those of Equations 4 and 5,which, relative to the quantity of transition metal present, have asmaller halogen content.

EQUATION 1 EQUATION 2 /-O Si-OH SiqOH /o /0 5 si-orr Si-OH 0 /o (31/0181 011 W615 j SiO-W-O1 21101 o 0 c1 c1 Si-OH SiO O /O $1 011 SiOHEQUATION 3 2O $1 0K SiOH /O /O SiOH Si O o /o 01 $1 011 W016 SiO-WCI3EOI 0 /0 c1 Si0H Si O 9 0O si ort S1 OH \O O EQUATION 4 O 0 SiOHSi-OH Si0H sf o Si OH W016 :2 Si-O-W-Ol 4HCl si ofl Si O o /o Si OI-ISi\-O EQUATION 5 \O \O Si OH Si O o /0 Si OH Si O O /O si on won :2 SiOWCl 5HC1 /O O si oH- Si-O O /O $1 011 si\ 0 O O On the other hand, ifmore transition metal compound is introduced than will react under thereaction conditions used, the excess is preferably removed beforeformation of the polymerization catalyst. Although the excess can beremoved by extraction, it is obviously more desirable to avoidadditional steps.

Organometallic compounds suitable for the purposes of the presentinvention are any of the compounds conforming to the general formula:

MM' X R v wherein M is a metal chosen from groups I, II or IE of theperiodic'table; M is a metal of group I of the periodic table; v equals0 or 1; each X is a halogen; n equals 0, l, 2, or 3 each R is anymonovalent hydrocarbon radical or hydrogen; and y equals 1, 2, 3 or 4.

Compounds of a single group I, II or III metal which are suitable forthe practice of the invention include c0ni-,

pounds-conforming to the subgeneric formula:

wherein M is a group I, II or III metal, such as lithium, sodium,beryllium, barium, boron, aluminum, copper,- Zinc, cadmium, mercury, andgallium; wherein k equals 1, 2 or 3 depending upon the valency of Mwhich valency in turn depends upon the particular group (i.e. I, II orIII) to which M belongs; and wherein each R may be any monovalenthydrocarbon radical. Examples of suitable R groups include an aryl oralkaryl radical, aliphatic hydrocarbon radical or derivative, such asalkyl, cycloalkylalkyl, cycloalkenylalkyl, arylalkyl, cycloalkyl,alkylcycloalkyl, arylcyclo alkyl, cycloalkylalkenyl.

Specific examples of R groups for substitution in the above formulainclude methyl, ethyl, n-propyl, isobutyl, n-amyl, isoamyl, hexyl,n-octyl, n-dodecyl, and the like; Z-butenyl, Z-methyl-Z-butenyl and thelike; cyclopentylmethyl, cyclohexylethyl, cyclopentylethyl,methylcyclopentylethyl, 4-cyclohexenylethyl and the like; 2-phenylethyl,Z-phenylpropyl, ez-naphthylethyl, methylnaphthylethyl, and the like;cycl-ophentyl, cyclohexyl, 2,2,1-bicycloheptyl, and the like;methylcyclopentyl, dimethylcyclopentyl, ethylcyclopentyl,methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl,isopr-opylcyclohexyl, S-cyclopent-adienyl, and the like;phenylcyclopentyl, phenylcyclohexyl,

and the corresponding naphthyl derivatives of cycl-oalkyl groups, andthe like; phenyl, tolyl, xylyl, ethylphenyl, xenyl, naphthyl,methylnaphthyl, dimethylnaphthyl, ethylnaphthyl, and cyclohexylphenyl.

Generally preferred, however, are the organocompounds of groups I, IIand III, such as methyl and buty1- lithium, pentenylsodium,dihexylmercury, diallylmagnesium, diethylcadmium, benzylpotass-ium,divinylmagnesium, di-ptolylmercury, diethylzinc, tri-n-butylaluminum,methyl phenyl mercury, diisobutyl ethylboron, diethylcadmium,di-n-butylzinc and tri-n-amylboron, and in particular and thealuminumalkyls, such as trihexylalurrrinum, triethylalum-inum,trimethylaluminum, and in particular tri-, isobutylaluminum.

In addition, mono-organo-halides and hydrides of group II metals, andmonoor di-organ-o-hal-ides and hydrides of group III metals conformingto the above general formula are also preferred. Specific examples ofsuch compounds are diisobutylaluminum bromide, isobutylboron dichloride,methylmagnesium chloride, phenylmercuric iodide, ethylberylliumchloride, ethylcalcium bromide, hexylcupric chloride, diisobutylaluminumhydride, methylcadmium hydride, diethylboron hydride, hexylberylliumhydride, dipropylboron hydride,voctylmagnesium hydride,

butylzinc hydride, dichloroboron hydride, dibromoalum-inum hydride andbromocadmium hydride. V

Also, compounds comprising a group I, II or III metal compound complexedwith a group I metal compound if they conform to the above generalformula, are generally suitable. Examples of such compounds aretetraethyllithium aluminum, tetrahexyllithium aluminum,trihexylpotassium aluminumchloride, triethyllithium aluminum bromide,tributylsodium zinc, tributyllith-ium zinc, trioctadecylpotassiumaluminum hydride, diphenyldilithium and diphenylp otassium lithium.

Although it is appreciated that when R, in the above defined generalformula, does not comprise at least one hydrocarbon radical, the groupI, II and III metal compounds of the present invention can not normallybe termed \organometallic compounds, compounds lacking at least onehydrocarbon radical comprise such a relatively small number of the totalnumber of compounds included by said general formula. that for thepurposes of the present invention, it is intended that these compoundsbe included within the generic term, organometallic compound.Accordingly, in the specification and in the claims, it is intended, andtherefore it should be understood, that the term, organonietalliccompound, refers to all the compounds included within the scope of theabove defined general formula.

Using the catalysts of this invention, polymerization of the olefiniccharging stock can be accomplished in the absence of liquids, solventsor diluents, for example, in the gas phase, but it is usually easier toeffect polymerization in the presence of a substantially inert liquidreaction medium which functions as partial solvent for the mgnomer, a.solvent for the organometallic compound, as a heat transfer agent, andas-a liquid transport medium to remove normally solid polymerizationproducts as a dispersion from the polymerization reactor, thuspermitting efficient and continuous polymerization operations.Accordingly, an inert liquid reaction medium is preferably supplied tothe reaction zone.

Several classes of hydrocarbons or their mixtures which are liquid andsubstantially inert under polymerization conditions of the presentprocess constitute suitable liquid reaction media. Thus, various classesof saturated hydrocarbons such as pure alkanes or cycloalkanes orcommercially available mixtures, freed of harmful impurities, aresuitable for the purposes of the present invention. vFor example,straight run naphthas or kerosenes containing alkanes and cycloalkanesand liquid or liquefid alkanes such as propane, butanes, n-pentane,n-hexene, 2,3-dimethylbutane, n-octane, isooctane(2,2,4-triniethylpentane), n-decane, n-dodecane, cyclohexane,methylcyclohexane, dimethylcyclopentane, ethylcyclohexane, decalin,methyldecalins, dimethyldecalins and the like are suitable. Also membersof the aromatic hydrocarbon series, such as ethylbenzene,isopropylbenzene, sec-butylbenzene, t-butylbenzene, ethyltoluene,ethylxylenes, hemimellitene, pseudocumene, perhnitene, isodurene,diethylbenzenes, isoamylbenzene, and particularly the mononucleararomatic hydrocarbons such as benzene, toluene, xylenes, mesitylene andxylene-p-cymene mixtures, and the like are completely suitable. Aromatichydrocarbon fractions obtained by the selective extraction of aromaticnaphthas, from hydroforming operations such as distillates or bottoms,from cycle stock fractions or cracking operations, etc., and certainalkyl naphthalenes which are liquid under the polymerization reactionconditions, for example, l-methyl-naphthalene, 2-isopropylnaphthalene,l-n-amylnaphthalene and the like, or

commercially produced fractions containing these hydrocarbons and thelike are also suitable.

The proportion of surface reacted particulate inorganic solid toorganometallic compound utilized in preparing the catalyst is notusually a critical feature of the process. Moreover, if this proportionis expressed as a simple molar or weight ratio, it may not beparticularly meaningful because, as indicated above, theefiiciency ofsaid surface reacted solids (on a weight or molar basis) is highlydependent upon the proportion of transition metal halide chemicallycombined therewith and the manner in which each atom of transition metalis chemically combined. Accordingly, in order to be most meaningful therelationship between catalyst components should be expressed as afunction of the amount of transition metal compound which has reactedwith the surface of the finely divided solid. We have found fromexperience that a molar ratio of from 0.1 to 3 mols of theorganometallic compound per mol of transition metal chemically combinedwith the surface of the finely divided solid is to be preferred.

The quantity of catalyst i.e., comprising both the surface reactedfinely divided solid and the organometallic compound, to be utilized inthe polymerization reaction may vary, the precise proportion selectedfor use being dependent upon the desired rate of polymerization, thegeometry of the reaction zone, the composition of the particularolefinic charging stock, temperature and other reaction variables. Itshould be pointed out that in general the efficiency of the catalysts ofthe present invention is extremely high and accordingly, the totalquantity of catalyst that need be employed based on the weight of thecharging stock is very small particularly when (a) a very fine particlesize oxide has been utilized as the inorganic solid and (b) thetransition metal halide reaction has been conducted in such a manner asto leave at least two halogen atoms on each transition metal atom.

Harmful impurities in the liquid hydrocarbon reaction medium can beeffectively neutralized prior to the formation therein, or additionthereto, of the catalyst or catalyst components by treating the liquidmedium with a etal alkyl as set forth in US. Patent No. 2,991,157, toAdam Orzechowski and James MacKenzie. The olefinic charging stocks canbe purified by any known means such as bubbling said stocks through asolution of a metal alkyl in a hydrocarbon solvent prior to theirintroduction into the polymerization reactor.

Temperature control during the course of the polymerization process canbe readily accomplished when a liquid hydrocarbon diluent is utilizedbecause of the presence in the reaction zone of a large liquid masshaving relatively high heat capacity. The liquid hydrocarbon reactionmedium can be cooled by heat exchange inside or outside the reactionzone.

The contact time or space velocity employed in the polymerizationprocess will be selected with reference to the other process variablesuch as the particular catalysts utilized, the specific type of productdesired, and the extent of olefin conversion desired in any given run orpass over the catalyst. In general, this variable is readily adjustableto obtain the desired results.

There follow a number of illustrative non-limiting examples:

Example 1 To a 1000 milliliter, three neck, glass reaction vessel therewas added 10 grams of Cab-o-sil, a pyrogenic silica produced by GodfreyL. Cabot, Inc. which has an average particle diameter of about 20millimicrons and a hydroxyl group content (based on ignition losses ofdry material) on the surface thereof of between about 2.3 and 2.7milliequivalents/gram. Said reaction vessel was then placed in a vacuumdrying oven heated to a temperature of about C. for about twelve hours.Subsequently, the vessel was sealed without exposing said silica to theatmosphere, and there were charged to said vessel 9.8 millimoles oftitanium tetrachloride and 500 milliliters of isooctane. The vessel wasthen continuously stirred, and heated to, and maintained at therefluxing temperature of isooctane for a period of 2.3 hours, while theHCl produced was continuously removed by sweeping the reactor vesselwith purified nitrogen; Subsequently, the extent of the reaction betweenthe titanium tetrachloride and the silica was determined by measuringthe quantity of HCl removed from the vessel by the nitrogen stream andby testing the liquid contents of the vessel for the absence therein oftitanium tetrachloride, and the said silica was found to have 9.8x l0gram atoms of titanium chemically bound to the surface thereof. 0.25grams of this surface reacted silica containig about 0.25 X 10- gramatoms of titanium on the surface thereof, and suspended in about 12milliliters of isooctane was then transferred without exposure to theatmosphere from this reaction vessel to a 500 milliliter, three neck,glass reaction vessel which had been previously flushed with drynitrogen. 88 milliliters of isooctane was then charged to this secondvessel and the vessel was saturated with ethylene. Next, 025 millimolesof triisobutyl aluminum was added and the contents of said secondreaction vessel were continuously and vigorously stirred, and ethylenewas continuously swept through the reaction vessel at a rate somewhatfaster than its consumption for about four hours. The reaction productswere analyzed and it was found that 37.2 grams of polyethylene which hada density of about 0.96 had been produced. The polymer product was apowdery material and was found to have a crystalline melting point ofabout 130135 C. It was further found that none of the ethylene had beenconverted to a normally liquid product.

Example 2 This example was a duplicate of Example 1, except that thesilica was not dried prior to treatment with the titanium tetrachloride.Also, although the treatment between the silica and the titaniumtetrachloride took place under a nitrogen atmosphere, the reactionvessel was not continuously swept with a nitrogen stream, as was done inExample 1, and accordingly no HCl was removed from the vessel during theperiod that the treatment took place. The treatment was carried out atroom temperature for 30 minutes. The catalyst was then formed as inExample 1 and utilized in a polymerization reaction as in Example 1. Thereaction products were analyzed and it was found that only 4.9 grams ofpolyethylene had been produced. 7

, Example 3 This example was a duplicate of Example 2, except that (a)during the treatment of the silica with the titanium tetrachloride, thereaction vessel was continuously swept with a nitrogen stream and (b)the treatment was carried out at 100 C. for 30 minutes rather than atroom temperature. Following formation of the catalyst and the usethereof in a polymerization reaction, all as described in Example 1,-the reaction product was analyzed; it was found that 5.1 grams ofpolyethylene had been produced.

Example 4 To a 2,000 milliliter, three neck, glass reaction vessel therewas added 20 grams of Cab-o-sil silica. Said reaction vessel was thenplaced in a vacuum drying oven heated to a temperatureof aboutv 110 C.,for about twelve hours. Subsequently, the vessel was sealed withoutexposing said silica to the atmosphere and there were charged to saidvessel 19.6 millimoles of titanium tetrachloride and 1,100 millilitersof isooctane. The vessel was then continuously stirred, and heated to,and maintained at, the refluxing temperature of isooctane for a periodof 3 hours, while the HCl produced was continuously removed by sweepingthe reactor vessel with purified nitrogen. Subsequently, the extent ofthe reaction between the titanium tetrachloride and the silica wasdetermined by measuring the quantity of HCl removed from the vessel bythe nitrogen stream, and by testing the liquid contents of the vesselfor the absence therein of titanium tetrachloride, and the said silicawas found.

to have 196x10 gram atoms of titanium chemically bound to the surfacethereof. 0.5 gram of this surface reacted silica containing about 5 gramatoms of titanium on the surface thereof, and suspended in about 25.5milliliters of isooctane was then transferred without being exposed tothe atmosphere from this reaction vessel to a second 2,000 milliliter,three neck, glass reaction vessel which had been previously flushed withdry nitrogen. 75 milliliters of isooctane was then charged to thissecond vessel and the vessel was saturated with ethylene. Next, 0.25millimoles of triisobutyl aluminum was added and the contents of saidsecond reaction vessel were continuously and vigorously stirred, andethylene was continuously swept through the reaction vessel at a ratesomewhat faster than its consumption for about four hours. The reactionproducts were analyzed and it was hours.

atmosphere for about 5 minutes, after which time the It) found that 93.9grams of polyethylene had been pro duced. 1'

Example 5 To a 1000 milliliter, three neck, glass reaction vessel therewas added 10 grams of Cab-o-sil silica. Said reaction vessel was thenplaced in a vacuum drying oven heated to a temperature 'of about C., forabout 12 Subsequently, the vessel was exposed .to the and the silica wasdetermined by testing the liquid contents of the vessel and finding thecomplete absence therein of titanium tetrachloride; the said silicatherefore was determined to have 7X10 gram atoms of titanium adsorbed onthe surface thereof. 0.67 grams of this silica containing about 5 10-gram atoms of titanium adsorbed on the surface thereof, and suspended inabout 33.5 milliliters of isooctane was then transferred from thisreaction vessel without exposure to the atmosphere to a 500 milliliter,three neck, glass reaction vessel which had been previously flushed withdry nitrogen. 66.5 milliters of isooctane was then charged to thissecond vessel and the vessel was saturated with ethylene. Next 0.25millimoles of triisobutyl aluminum was added and the contents of saidsecond reaction vessel were continuously and vigorously stirred, andethylene was continuously swept through the reaction vessel for about 4hours. The reaction products were analyzed and it was found that nopolyethylene had been produced.

Example 6 To a 1,000 milliliter, three neck, glass reaction vessel therewas added 10 grams of Cab-o-sil silica. Said reaction vessel was thenplaced in a vacuum drying oven heated to a temperature of about 110 C.,for about twelve hours. Subsequently, the vessel was sealed withoutexposing said silica to the atmosphere and there were charged to saidvessel 7.4 millimoles of titanium tetrachloride and 500 milliliters ofisooctane. The vessel was then continuously stirred and was maintainedat room temperature for a period of 1 hour under conditions such that noHCl was removed (the reactor was not swept with nitrogen during thereaction). Subsequently, the extent of the reaction between the titaniumtetrachloride and the silica was determined by measuring the amount oftitanium tetrachloride found in the supernatant liquid and the saidsilica was found to have 7.4 10 gram atoms of titanium adsorbed on thesurface thereof. 0.67 gram of this treated silica having about 5 10 gramatoms of titanium adsorbed on the surface thereof, and suspended inabout 33.5 milliliters of isooctane was then transferred withoutexposure to the atmosphere from this reaction vessel to a 500milliliter, three neck, glass reaction vessel which had been previouslyflushed with dry nitrogen. 66.5 milliliters of isooctane was thencharged to this second vessel and the vessel was saturated withethylene. Next, 0.25 millimole of triisobutyl aluminum was added and thecontents of said second reaction vessel were continuously and vigorouslystirred, and ethylene was continuously swept through the reaction vesselat a rate somewhat faster than its consumption for about four hours. Thereaction products were analyzed and it was found that 22.6 grams ofpolyethylene had been produced.

Example 7 To a 1000 milliliter, three neck, glass reaction vessel therewas added 10 grams of Cab-o-sil silica. Said 1 l reaction vessel wasthen placed in a vacuum drying oven heated to a temperature of about 110C., for about twelve hours. Subsequently, the vessel was sealed withoutexposing said silica to the atmosphere and there were charged to saidvessel 7.4 millimoles of titanium tetrachloride and 530 milliliters ofisooctane. The vessel was then continuously agitated and maintained atroom temperature for a period of 0.5 hour, while the HCl produced wascontinuously removed by sweeping the reactor vessel with purifiednitrogen. Subsequently, the extent of the reaction between the titaniumtetrachloride andthe silica was determined by measuring the quantity ofHCl re moved from the vessel by the nitrogen stream, and by testing theliquid contents of the vessel for the absence therein of titaniumtetrachloride, and the said silica was found to have 7.4 lgram atoms oftitanium chemically bound to the surface thereof. 0.695 of this silicacontaining about 5 10 gram atoms of titanium chemically bound to thesurface thereof, and suspended in about 24.6 milliliters of isooctanewas then transferred without exposure to the atmosphere from thisreaction vessel to a 500 milliliter, three neck, glass reaction vesselwhich had been previously flushed with dry nitrogen. 65.4 milliliters ofisooctane was then charged to this second vessel and the vessel wassaturated with ethylene. Next, 0.25 millimole of triisobutyl aluminumwas added and the contents of said second reaction vessel werecontinuously and vigorously stirred, and ethylene was continuously sweptthrough the reaction vessel at a rate somewhat faster than itsconsumption for about four 0 hours. The reaction products were analyzedand it was found that 75 grams of polyethylene had been produced.

Example 8 To a 1000 milliliter, three neck, glass reaction vessel therewas added 10 grams of P- titania, a pyrogenic titania produced byDeutsche Gold-Und Silber-Scheideanstalt Vormals Roessler, Germany, whichhas an average particle diameter of about 20 millimicrons and a hydroxylgroup content on the surface thereof (as measured by ignition losses ofdry titania) of between about 1 and 1.4 milliequivalents/gram. Saidreaction vessel was then placed in a vacuum drying oven heated to atemperature of about 110 C., for about twelve hours. Subsequently, thevessel was sealed without exposing said titania to the atmosphere andthere were charged to said vessel 2.8 millimoles of titaniumtetrachloride and 500 milliliters of isooctane. The vessel was thencontinuously agitated,

and heated to, and maintained at the refluxing temperature of isooctanefor a period of 3 hours, while the HCl produced was continuously removedby sweeping the reactor vessel with purified nitrogen. Subsequently, theextent of the reaction between the titania and the titaniumtetrachloride was determined by measuring the quantity of HCl removedfrom the vessel by the nitrogen stream, and by determining the titaniumtetrachloride content of the supernatant liquid and the said titania wasfound to have 2.8 10* gram atoms of titanium chemically bound to thesurface thereof. 0.84 gram of this titania containing about 2.5 l0 gramatoms of titanium on the surface thereof, and suspended in about 42milliliters of isooctane was then transferred without being exposed tothe atmosphere from this reaction vessel to a 500 milliliter, threeneck, glass reaction vessel which had been previously flushed with drynitrogen. 58 milliliters of isooctane was then charged to this secondvessel and the vessel was saturated with ethylene. Next, 0.25 millimoleof triisobutyl aluminum was added and the contents of said secondreaction vessel were continuously and vigorously stirred, and ethylenewas continuously swept through the reaction vessel at a rate somewhatfaster than its consumption for about 4.5 hours. The reaction productswere analyzed and it was found that 29.5 grams of polyethylene had beenproduced.

-milliliters of isooctane.

Example 9 To a 1000 milliliter, three neck, glass reaction vessel therewas added 10 grams of l-li-Sil-X-303, a precipitated silica produced byColumbia Southern Chemical Corp., and which has an average particlediameter of about 23 miilimicrons and a hydroxyl group content on thesurface thereof (as measured by ignition losses of the dry silica) ofabout 4.3 milliequivalents/gram. Said reaction vessel was then placed ina vacuum drying oven heated to a temperature of about C., for abouttwelve hours. Subsequently, the vessel was sealed Without exposing saidsilica to the atmosphere and there were charged to said vessel 5.6millimoles of titanium tetrachloride and 500 milliliters of isooctane.The vessel was then continuously agitated and heated to, and maintainedat the refluxing temperature of isooctane for a period of 3.5 hours,while the HCl produced was continuously removed by sweeping the reactorvessel with purified nitrogen. Subsequently, the extent of the reactionbetween the titanium tetrachloride and the silica Was determined bymeasurin the quantity of HCl removed from the vessel by the nitrogenstream, and by testing the liquid contents of the vessel for the absencetherein of titanium tetrachloride, and the said silica was found to have5.6 l0 gram atoms of titanium chemically bound to the surf ce thereof.0.42 gram of this silica containing about Z..5 l0 gram atoms of titaniumchemically bound to the surface thereof, and suspended in about 21milliliters of isooctane was then transferred without exposure to theatmosphere from this reaction vessel to a 500 milliliter, three neck,glass reaction vessel which had been previously flushed with drynitrogen. 79 milliliters of isooctane was then charged to this secondvessel and the vessel was saturated with ethylene. Next, 0.25 millimoleof triisobutyl aluminum was added, and the contents of said secondreaction vessel were continuously and vigorously stirred, and ethylenewas continuously swept through the reaction vessel at a rate somewhatfaster than its consumption for about 1.75 hours. The reaction productswere analyzed and it was found that 17.9 grams of polyethylene had beenproduced.

Example 1 0 To a 500 milliliter, three neck, glass reaction vessel therewas added 5 grams of Alon, a pyrogenic alumina produced by DeutscheGold-Und Silber-Scheideanstalt Vorrnals Roessler which has an averageparticle diameter of about 10-4O millimicrons. Said reaction vessel wasthen placed in a vacuum drying oven heated to a temperature of about 110C., for about twelve hours. Subsequently, the vessel was sealed withoutexposing said alumina to the atmosphere and there were charged to saidvessel 4.7 millimoles of titanium tetrachloride and 250 The vessel wasthen continuously stirred and heated to, and maintained at the refluxingtemperature of isooctane for a period of 4 hours, while the HCl producedwas continuously removed by sweeping the reactor vessel with purifiednitrogen. Subscquently, the extent of the reaction between the aluminaand the titanium tetrachloride was determined by measuring the quantityof HCl removed from the vessel by the nitrogen stream, and by testingthe liquid contents of the vessel for the absence therein of titaniumtetrachloride, and the said alumina was found to have 2.7 l0 gram atomsof titanium chemically bound to the surface thereof. The excess titaniumtetrachloride was removed by washing With isooctane. 0.44 grams of thisalumina containing about 2.5 x 10* gram atoms of titanium chemicallybound to the surface thereof, and suspended in about 22 milliliters ofisooctane was then transferred from this reaction vessel to a second 500milliliter, three neck, glass reaction vessel which had been previouslyflushed with dry nitrogen. 78 milliliters of isooctane was 13 thencharged to this second vessel and the vessel, was saturated withethylene.

second reaction vessel were continuously and vigorously stirred, andethylene was continuously swept through the reaction vessel at a ratesomewhat faster than its consumption for about four hours. The reactionproducts Next, 0.25 -millimoles of triisobutyl'alurninum was addedandthe contents'of said were analyzed and it was found that 22.5 gramsof poly:

ethylene had been produced.

Example 11 To a 1000milliliter, three neck, glass reaction vessel therewas added 10 grams of Cab-o-sil silica. Said reaction vessel was thenplaced in a vacuum drying oven heated to a temperatureof about 110 C.,for about twelve hours. Subsequently, the vesselwassealed with-'outexposing said silica to the atmosphere and there were charged tosaid vessel 6 millimoles of titanium tetrachloride and 530 millilitersof isooctane. The vessel was then continuously stirred and heated to,and maintained at the refluxing temperature of isooctane for a period ofatoms of titanium chemically bound to the surface thereof. 0.85 grams ofthis silica containing about 5X10 gram atoms of titanium chemicallybound to the surface thereof, and suspended in about 42.8 milliliters ofisooctane was then transferred from this reaction vessel to a 500milliliter, three neck, glass reaction vessel which had been previouslyflushed with dry nitrogen. 57.2 milliliters of isooctane Was thencharged to this second ves sel and the vessel was saturated withethylene. Next, 0.25 millimoles of triisobutyl aluminum were added andthe contents of said second reaction vessel were continuously'andvigorously stirred, and ethylene was continuously swept through thereaction vessel at a rate somewhat faster than its consumption for aboutfour hours. The reaction products were analyzed and it was found that49.7 grams of polyethylene had been produced.

Example 12 To a 1000 milliliter, three neck, glass reaction vessel therewas added grams of Cab-o-sil silica. Said reaction vessel was thenplaced in a vacuum drying oven heated'to a temperature of about 110 C.,for about twelve hours. out exposing said silica to the atmosphere andthere were charged to said vessel 8.5 millimoles" of titaniumtetrachloride and 530 milliliters of isooctane. The vessel was thencontinuously agitated and maintained at C., for a period of 10 hours,while the HCl produced Was continuously removed by sweeping the reactorvessel with purified nitrogen. Subsequently, the extent of the reactionbetween the titanium tetrachloride and the silica was determined bymeasuring the quantity of HCl removed from the vessel by the nitrogenstream, and by testing the liquidcontents of the vesselfor the absencetherein of titanium tetrachloride, and the said silica-was found to have8.5 10 gram atoms of titanium chemically bound to' the surface thereof.0.59 gramsof this silica'containing about 5 10* gram atoms of titaniumchemically bound to the surface thereof, 'and suspended in about 29.4milliliters of isooctane was then transferred from this reaction vesselto a 500 milliliter, three neck, glass reaction vessel which had beenpreviously flushed with dry nitrogen. 70.6 milliliters of isooctane wasthen charged to this second vessel and the vessel was saturated withethylene. -Next, 0.25 millimoles of triisobutyl alu minum Was added andthe contents of said second reac- "14 tion vessel were continuously andvigorously stirred, and ethylene was continuously swept'through thereaction vessel ata rate somewhat faster than its consumption for aboutfour hours. The reaction products were analyzed and it was found that93.6 grams of polyethylene had been produced.

Example 13 To a 1,000 milliliter, a three neck, glass reaction'vesselSaid there was added 10 grams of Cab-o-silVsilica. reaction vessel wasthen placed in .a vacuum drying oven heated to a temperature of about110 C., for about twelve hours. Subsequently, the vesselwas sealedwith.- out exposing said silica to the atmosphere and there were chargedto said vessel 11.5 millimoles of finely divided zirconium tetrachlorideand '500 milliliters of benzene. The vessel was then heated to, andmaintained at the refluxing temperature of benzene for a period of '6hours, while the HCl produced was continuously re- Subsequently, thevessel was sealed withmoved by sweeping the reactor vessel with purifiednitrogen. The nitrogen stream was analyzed and it was found that 17milliequivalents of HClhad been removed from the vessel. 0.43 grams ofthis silica containing about 5 10 gram atoms of zirconium chemicallybound to the surface thereof, and suspended in about 20.4 milliliters ofisooctane was then transferred from this reaction vessel to a second1,000 milliliter, three neck, glass reaction vessel which had beenpreviously flushed with dry nitrogen.

was added and the contents of said second reaction vessel werecontinuously and vigorously stirred and ethylene was continuously sweptthrough the reaction vessel at a rate somewhatfaster than itsconsumption for about The reaction products were analyzed and fourhours.

it was found that 101 grams of polyethylene had been produced.

Example 14 To a 500 milliliter, three neck, glass reaction vessel whichhad previously been flushed with dry nitrogen there was charged 0.5millimoles of finely divided zirconium tetrachloride (the same as usedin Example 13 above) and'100'milliliters'of isooctane. Next, 0.25millimoles of triisobutyl aluminum was added, the vessel was saturatedwith ethylene, the contents of said reaction vessel were continuouslyand vigorously stirred, and ethylene was continuously swept through thereaction vessel for about 4 hours. There was no visible reaction and nopolyethylene was produced.

Example 15 tetrachloride (the same as utilized in Example 13) and 500milliliters of isooctane. The vessel was thenjmaintained at roomtemperature for a period of0.5 hours, during which time, unlike theprocedure in Example 13, the reactor vessel was notswept by a stream ofnitrogen. 20.4 millimoles of this slurry containing 0.43 grams of silicaand 0.5 millimoles of zirconium tetrachloride which was not bound to thesilica, was then transferred Without exposure toa tmosphere from thisreaction vessel to a.

second 1,000 milliliter, three neck, glass reaction vessel which hadbeen previously flushed with dry nitrogen.

milliliters of isooctane was then charged to this second vessel and thevessel was saturated with ethylene. Next, 0.25 millimoles of triisobutylaluminum was added and the contents of said second reaction vesselv werecontinuously and vigorously stirred, and ethylene was 179.6 millilitersof isooctane was then charged to. this second vessel and the vessel wassaturated with ethylene. Next, 0.25 millimoles of triisobutyl aluminumthere was added 10 grams of Cab-o-sil silica.

500 milliliters of isooctane.

Example 16 To a 1,000 milliliter, three neck, glass reaction vessel Saidreaction vessel was then placed in an oven heated to a teinperature ofabout 110 C., for about twelve hours. Subsequently, the vessel wassealed without exposing said silica to the atmosphere and there werecharged to said vessel 11.5 millimoles of finely divided zirconiumtetrachloride (the same as utilized in Example 13), and

The vessel was then maintained at the refluxing temperature ofisooctanefor a period of hours, while the HCl produced was continuouslyremoved by sweeping the reactor vessel with purified nitrogen. the flaskwas determined to be 17 milliequivalents. 0.43 grams of this silicacontaining about 0.5 millimoles of zirconium partly bound and partlyadsorbed on the surface thereof, and suspended in about 20.4 millilitersof isooctane was then transferred from this reaction vessel to a 500milliliter, three neck, glass reaction vessel which had been previouslyflushed with dry nitrogen. 180 milliliters of isooctane was then chargedto this second vessel and the vessel was saturated with ethylene. Next,0.25 millimoles of triisobutyl aluminum was added and the contents ofsaid second reaction vessel were continuously and vigorously stirred,and ethylene was continuously swept through the reaction vessel at arate somewhat faster than its consumption for about four hours. Thereaction products were analyzed and it was found that 32.5 grams ofpolyethylene had been produced.

Example '17 To a 2,000 milliliter, three neck, glass reaction vesselthere was added 25 grams of Cab-o-sil silica. Said reaction vessel wasthen placedin a vacuum drying oven heated ,to a temperature of about 110C for ab out twelve hours. Subsequently, the vessel was sealed withoutexposing said silica to the atmosphere and there were charged to saidvessel 24.5 millimoles of titanium tetrachloride and 1200 milliliters ofisooctane. The vessel was then continuously agitated and heated to, andmaintained at the refluxing temperature of isooctane for a period of 4hours, while the HCl produced was continuously removed by sweeping thereactor vessel with purified nitrogen. Subsequently, the extent ofreaction between the titanium tetrachloride and the silica wasdetermined by measuring the quantity of HCl removedfrorn the vessel bythe nitrogen stream, and by testing the liquid contents of the vesselfor the absence therein of titanium tetrachloride, and the said silicawas found to have 24.5 X gram atoms of titanium chemically bound to thesurface thereof. 1 gram of this silica containing about 1X 10- gramatoms of titanium chemically bound to the surface thereof, and suspendedin about 51 milliliters of isooctane was then transferred from thisreaction vessel to a 1,000 milliliter, three neck, glass reaction vesselwhich had been previously flushed with dry nitrogen. 200 milliliters ofisooctane was then charged to this second reaction vessel and the vesselwas saturated with ethylene. Next, 024 millimole of freshly distilledtriisobutyl aluminum was added and the contents of said second reactionvessel were continuously and vigorously stirred, and ethylene wascontinuously swept through the reaction vessel at a rate somewhat fasterthan its consumption for about four hours. The reaction products wereanalyzed and it was found that 140 grams of polyethylene had beenproduced.

Example 18 To a 1000 milliliter, three neck, glass reaction vessel therewas added 10 grams of Cab-o-sil silica. Said re- The quantity of HClremoved from action Vessel was then placed in a vacuum drying ovenheated to a temperature of about 110 C., for about twelve hours.Subsequently, the vessel was sealed without'exposing said silica to theatmosphere and there were charged to said vessel 8.5 rnillimoles oftitanium tetrachloride and 530 milliliters of isooctane. I The vesselwas then continuously agitated and maintained atroom temperature for aperiod of 10 hours, while the HCl produced was continuously removed bysweeping the reactor vessel with purified nitrogen. Subsequently, theextent of the reaction between the titanium tetrachloride and the silicawas determined by measuring the quantity ofI -lCl removed from thevessel by the nitrogen stream, and by testing the liquid contents of thevessel for the absence therein of'titaniu'm tetrachloride, and the saidsilica was found to. have 85x10 gram atoms of titanium chemically boundto the surface thereof. 0.59 gram of this silica containing about 5x10gram atoms of titanium chemically bound to the surface thereof, andsuspended in about 29.4 milliliters of isooctane was then transferredfrom this reaction vessel to a 500 milliliter, three neck, glassreaction vessel which had been previously flushed with dry nitrogen.70.6 milliliters of isooctane was then charged to this second vessel andthe vessel was saturated with ethylene. Next, 0.25 millimole of butyllithium was added and the contents of said second reaction vessel werecontinuously and vigorously stirred, and ethylene wascontinuously sweptthrough the reaction vessel at a rate somewhat faster than itsconsumption for about 0.5 hour. Then an additional 0.5 millirnole ofbutyl lithium was added to the reaction vessel and the reaction wascontinued as before for 315 more hours. The reaction prodacts wereanalyzed and it was found that 28.7 grams of polyethylene had beenproduced.

Example 19 To a 2,000 milliliter, three neck, glass reaction vesselthere was added grams of Cab-o-sil silica. Said reaction vessel was thenplaced in a vacuum drying oven of HCl removed from the vessel by thenitrogen stream,

and by testing the liquid contents of the vessel for the absence thereinof titanium tetrachloride, and the said silica was found to have 24.5l0- gram atoms of titanium chemically bound to the surface thereof. 1gram of this silica containing about 1X 10- gnam atoms of titaniumchemically bound to the surface thereof, and suspended in about 51milliliters of isooctane was then transferred without exposure to theatmosphere from this reaction vessel to a second 2,000 milliliter, threeneck, glass reaction vessel which had been previously flushed with drynitrogen. 200 milliliters of isooctane was then charged to this secondvessel and the vessel was saturated with ethylene. Next, 0.25 millimoleof freshly distilled triisobutyl aluminum was added and the contents ofsaid second reaction vessel were continuously and vigorously stirred,and ethylene was continuously swept through the reaction vessel at arate somewhat faster than its consumption for about four hours. Thereaction products were analyzed and it was found that 141 grams ofpolyethylene had been produced.

' there was added 5 grams of Cab-o-sil silica. Said reaction vessel wasthen placed in a vacuum drying oven heatedto a temperature of about 110C., for about twelve hours. Subsequently, the vesselwas sealed withoutexposing said silica to the atmosphere and there were charged to saidvessel millimoles of vanadium trichloride and 8 milliliters of methanol.The vessel was then continuously stirred, and maintained at roomtemperature for a period of 2 hours, while the HCl produced wascontinuously removed by sweeping the reactor vessel with purifiednitrogen. Subsequently, the extent of the reaction between the vanadiumtrichloride and the silica was determined by measuring the quantity ofHCl removed from the vessel by the nitrogen stream, and by testing theliquid contents of the vessel for the absence therein of vanadiumtrichloride and the said silica was found to have 5 10- gram atoms ofvanadium on the surface thereof. The vessel was then swept by a drybutheated nitrogen stream until all the methanol had evaporated. 250milliliters of isooctane was then added to the vessel in order toproduce a slurry therein. 100 milliliters of this slurry containingabout 2X10" gram atoms of vanadium trichloride bound to the surface of 2grams of silica, was then transferred from this reaction vessel to a 500milliliter, stainless steel bomb which had been previ: ously flushedwith dry nitrogen. triisobutyl aluminum and 120 grams of liquidpropylene were added and the bomb was continuously agitated in a 50 C.,water bath for about 90 hours. The reaction products were analyzed andit was found that 11.9 grams of polypropylene having a weight averagemolecular weight of about 450,000 and a crystalline melting point ofabout 170 C., had been produced,

Example 21 To a 1,000 milliliter, three neck,- glass reaction vesselthere was added grams of Cab-o-sil silica. Said re action vessel wasthen placed in a vacuum drying oven heated to a temperature of about 110C., for about twelve hours. Subsequently, the vessel was sealed withoutexposing said silica to the atmosphere and there were charged to saidvessel 10 millimoles of titanium tetrachloride and 530 milliliters ofbenzene. The vessel was then heated to'and maintained at about 100 C.for a period of 4 hours, while the HCl produced was continuously removedby sweeping the reactor vessel with purified nitrogen. Subsequently, theextent of the reaction between the titanium tetrachloride and the silicawas determined by measuring the quantityof HCl removed from the vesselby the nitrogen stream, and by testing the liquid contents of the vesselfor the absence therein of titanium tetrachloride, and the said silicawas found to have 10x10" gram atoms of titanium chemically bound to thesurface thereof. 1.85 grams of this silica containing about 2X10 gramatoms of titanium chemically boundto the surface thereof, and'suspendedin about 80 milliliters of benzene, was then transferred from thisreaction vessel to a 500 milliliter stainless steel bomb, which had beenpreviously evacuated and flushed with dry nitrogen. 20 milliliters ofbenzene was then charged to the bomb. Next, 2 millimoles of triisobutylaluminum and 100 grams of dry propylene were added, and the bomb wascontinuously rotated in a 50 C. water bath. The reaction products wereanalyzed and it was found that 79 grams of polypropylene had beenproduced.

Example 22 To a 1000 milliliter, three neck, glass reaction vessel therewas added 10 grams of Cab-o-sil silica. Said reaction vessel was thenplaced in :a vacuum drying oven heated to a temperature of about 110 C.,for about twelve hours. Subsequently, the vessel was sealed withoutexposing said silica to the atmosphere and there were charged to saidvessel 20 millimoles of titanium tetrachloride and 570 milliliters ofisooctane. The vessel was then agitated and maintained at roomtemperature for a Next, 2 millimoles of r 18 period of about 5. minutes,ously swept by aslow stream of purified nitrogen. The extent of reactionbetween the titanium tetrachloride and the silica was then determined bydetermining the titanium tetrachloride content of the supernatantsolution in the vessel and the HCl content of the nitrogen sweep stream.It was found that 8 moles of titanium tetrachloride had been adsorbedbut that substantially no HCl had been evolved. The mixture was nextallowed to stand overnight-without stirring or sweeping with nitrogen.Upon analysis it was found that substantially no change had occurred,i.e., no more titanium tetrachloride had been adsorbed and no HCl hadbeen produced.

The mixture was next continuously agitated and swept with dry nitrogenfor 6 hours. By analysis of the supernatant liquid, it was determinedthat an addition 2 millimoles of titanium tetrachloride had beenadsorbed. Moreover, and of even greater importance, analysis of thenitrogen sweep gas revealed that 13 milliequivalents of HCl had'beenproduced. The mixture was then re Example 23 To a 1,000 milliliter,three neck, glass reaction vessel there was added 30 grams of Cab-o-silsilica. Said reaction vessel was then placed in a vacuum drying ovenheated tosa temperature of about C., for about twelve hours. The vesselwas then sealed without exposing said silica to the atmosphere and therewere charged to said vessel 40.5 millimoles of titanium tetrachlorideand 700 milliliters of isooctanef. The vessel was then continuouslystirred and heated to, and maintained at the refluxing temperature ofisooctane for a period of 7 hours, while the HCl produced wascontinuously removed by sweeping the reactor'vessel with purifiednitrogen; The

extent ofthe reaction between the titanium tetrachloride and the silicawas determined by measuring the quantity of HCl removed from the vesselby the nitrogen stream, and by testing the liquid contents of the vesselfor the absence therein of titanium tetrachloride, and the said silicawas found to have 40.5 10 gram atoms of titanium chemically bound to thesurface thereof. 0.9 gram of this silica containing about 1.2 10 gramatoms of titanium chemically bound to the surface thereof, and suspendedin about 29 milliliters of isooctane was then transferred, without beingexposed to the atmosphere, from this reaction vessel to a 1,000milliliter stirred autoclave which had'been previously flushed with drynitrogen. .2 0 milliliters of isooctane, grams of liquid propylene To a1,000 milliliter, three neck, glass reaction vessel, there was added 20grams of Cab-o-sil silica. Said reaction vessel was then placed in avacuum drying oven heated to a temperature of about 110 C., for abouttwelve hours. Subsequently, the vessel was sealed withwhile the vesselwas continu-.

out exposing said silica to the atmosphere and there were charged tosaid vessel 28 millimoles of titanium tetrachloride and 600 millilitersof isooctane. The vessel was then heated to and maintainedat therefluxing temperature of isooctane for a period of 4 hours, while theHCl produced was continuously removed by sweeping the reactor vesselwith purified nitrogen. Subsequently, the extent of the reaction betweenthe titanium tetrachloride and the silica was determined by measuringthe quantity of HCl removed from the vessel by the nitrogen stream, andby testing the liquid contents of the vessel for the absence therein oftitanium tetrachloride, and the said silica was found to have 28 10 gramatoms of titanium chemically bound to the surface thereof. 0.8 gram ofthis silica containing about 1.2 l gram atoms of titanium chemicallybound to the surface thereof, and suspended in about 26 milliliters ofisooctane was then transferred without exposure to atmosphere from thisreaction vessel to a 12 ounce pop bottle which had been previouslyflushed with dry nitrogen. 125 milliliters of isooctane, 13.5 grams ofliquid butene and 3.3 grams of liquid propylene were then charged to thebottle. Next, 2 millimoles of triisobutyl aluminum was added and thebottle was then continuously and vigorously agitated in a 50 C. waterbath for about 19 hours. The reaction products were analyzed and it wasfound that 12 grams of a rubbery copolymer had been produced.

Example To a 2,000 milliliter, three neck, glass reaction vessel therewas added grams of Cab-o-sil silica. Said reaction vessel was thenplaced in a vacuum drying oven heated to a temperature of about 110 C.,for about twelve hours. Subsequently, the vessel was sealed withoutexposing said silica to the atmosphere and there were charged to saidvessel 40.5 millimoles of titanium tetrtachloride and 700 milliliters ofisooctane. The vessel was then heated to and maintained at the refluxingtemperature of isooctane for a period of 4 hours, while the I-IClproduced was continuously removed by sweeping the reactor vessel withpurified nitrogen. Subsequently, the extent of the reaction between thetitanium tetrachloride and the silica was determined by measuring thequantity of HCl removed from the vessel by the nitrogen stream and bytesting the liquid contents of the vessel for the absence therein oftitanium tetrachloride, and the said silica was found to have 40.5 l0gram atoms of titanium chemically bound to the surface thereof. 0.9 gramof this silica containing about 1.2 l0 gram atoms of titanium chemicallybound to the surface thereof, and suspended in about 29 milliliters ofisooctane was then transferred, without exposure to the atmosphere, fromthis reaction vessel to a 12 ounce pop bottle which had been previouslyflushed with dry nitrogen. milliliters of isooctane and about 13.0 gramsof liquid'butadiene were then charged to this second vessel. Next, 1millimole of triisobutyl aluminum was added and the bottle was thencontinuously and vigorously agitated in a 50 C. water bath for about 18hours. The reaction products were analyzed and it was found that 12.7grams of polybutadiene had been produced.

Example 26 To a 1,000 milliliter, three-neck, glass reaction vesselthere was added 20 grams of Cab-o-sil silica. Said reaction vessel wasthen placed in a vacuum drying oven heated to a temperature of about 110C., for about twelve hours. Subsequently, the vessel was sealed withoutexposing said silica to the atmosphere and there were charged to saidvessel 28 millimoles of titanium tetrachloride and 600 milliliters ofisooctane. The vessel was then heated to and maintained at the refluxingtemperature of isooctane for a period of 4 hours, while the HCl producedwas continuously removed by sweeping the reactor vessel with purifiednitrogen. Subsequently, the extent of the reaction between the titaniumtetrachloride and the silica was determined by measuring the quantity ofHCl removed from the vessel by the nitrogen stream, and by testing theliquid contents of the vessel for the absence therein of titaniumtetrachloride, and the said silica was found to have 28x10- gram atomsof titanium on the surface thereof. 0.8 gram of this silica containingabout 1.2 l0- gram atoms of titanium chemically bound to the surfacethereof, and suspended in about 26 milliliters of isooctane was thentransferred, without exposure to the atomsphere, from this reactionvessel to a 12 ounce pop bottle which had previously been flushed withdry nitrogen. 55 milliliters of isooctane and 28.2 grams of butene-lwere then charged to the bottle. Next, 1 millimole of triisobutylaluminum was added and the bottle was then continuously and vigorouslyagitated in a 50 C. Water bath for about 20 hours. The'reaction productswere analyzed and it was found that 24.5 grams of polybutene having aweight average molecular weight of about 250,000 and a crystallinemelting point of about 140 C. had been produced.

Example 27 To a 500 milliliter, three neck, glass reaction vessel thereis added 10 grams of Cab-o-sil silica. Said reaction vessel is thenplaced in a vacuum drying oven heated to a temperature of about C., forabout twelve hours. Subsequently, the vessel is sealed without exposingsaid silica to the atmosphere and there is charged to said vessel 10millimoles of titanium tetrabromide and 300 milliliters of isooctane.The vessel is then heated to and maintained at the refluxing temperatureof isooctane for a period of 10 hours, while the HBr produced iscontinuously removed by sweeping the reactor vessel with puriliednitrogen. Subsequently, the extent of the reaction between the titaniumtetrabromide and the silica is determined by measuring the quantity ofHBr removed from the vessel by the nitrogen stream, and by testing theliquid contents of the vessel for the absence therein of titaniumtetrabromide, and the said silica is found to have 10 X10- gram atoms oftitanium chemically bound to the surface thereof. 1 gram of this silicacontaining about 1X10 gram atoms of titanium chemically bound to thesurface thereof, and suspended in about 30 milliliters of isooctane isthen transferred, without exposure to the atmosphere, from this reactionvessel to a second 500 milliliter, three neck, glass reaction vesselwhich has been previously flushed with dry nitrogen. 70 milliliters ofisooctane is then charged to this second vessel and the vessel issaturated with ethylene. Next, 0.5 millimole of aluminum diethylchloride is added and the contents of said second reaction vessel arecontinuously and vigorously stirred, and ethylene is continuously sweptthrough the reaction vessel at a rate somewhat faster than itsconsumption for about four hours. The reaction products are analyzed andit is found that about 87 grams of polyethylene have been produced.

Example 28 To a 500 milliliter, three neck, glass reaction vessel therewas added 10 grams of Cab-o-sil silica. Said reaction vessel was thenplaced in an oven heated to a temperature of about 110 C., for abouttwelve hours. Subsequently, there were charged to said vessel 9.8millimoles of titanium tetrachloride and 250 milliliters of isooctane.The vessel was then heated to and maintained at the refluxingtemperature of isooctane for a period of 4 hours, while the HCl producedwas continuously removed by sweeping the reactor vessel with purifiednitrogen. Subsequently, the extent of the reaction between the titaniumtetrachloride and the silica was determined by measuring the quantity ofHCl removed from the vessel by the nitrogen stream, and by testing theliquid contents of the vessel for the absence therein of titaniumtetrachloride and the said silica was found to have 9.8 10 gram atoms oftitanium chemically bound to the surface thereof.

. 21 2.24 grams of this silica containing about 2'.2 1t)- gram atoms oftitanium chemically bound to the surface thereof, and suspended in about56 milliliters of isooctane was then transferred, without exposure tothe atmosphere, from this reaction vessel to a 12 ounce pop bottle whichhad been previously flushed with dry nitrogen. 94 milliliters ofisooctane, and 36 grams of styrene were then charged to the bottle.Next, 2.6 millimoles of triisobutyl aluminum was added and the bottlewas continuously and vigorously agitated in a 25 C. air bath for about90 hours. The reaction products were analyzed and it was found that 5grams of polystyrene which was 40% soluble in boiling methyl ethylketone had been produced.

Example 29 To a 500 milliliters, three neck, glass reaction vessel therewas added grams of Cab-o-sil silica. Said reaction vessel was thenplaced in an oven heated to a temperature of about 110 C., for abouttwelve hours. Subsequently, there were charged to said vessel 9.8millimoles of titanium tetrachloride and 250 milliliters of isooctance.The vessel was then heated to and maintained at the refluxingtemperature of isooctane for a period of 4 hours, while the HCl producedwas continuously removed by sweeping the reactor vessel with purifiednitrogen. Subsequently, the extent of the reaction between the titaniumtetrachloride and the silica was determined by measuring the quantity ofHCl removed from the vessel by the nitrogen stream, and by testing theliquid contents of the vessel for the absence therein of titaniumtetrachloride, and the said silica was found to have 9.8 10- gram atomsof titanium chemically bound to the surface thereof; 0.41 gram of thissilica containing about 4 10 gram atoms of titanium chemically bound to.the surface thereof, and suspended in about 10.2-milliliters ofisooctane was then transferred, without exposure to the atmosphere, fromthis reaction vessel to a 12 ounce pop bottle which hadbeen previouslyflushed with dry nitrogen. 140 millititers of isooctane and 16.7 gramsof isoprene were then charged to the bottle. Next, 2 millimoles oftriisobutyl aluminum was added and the bottle was continuously andvigorously agitated in a 25 C. air bath for about 113 hours. Thereaction products were analyzed and it was found that 11 grams ofrubbery polyisoprene had been produced.

' i Example 30 continuously agitated and heated to, and maintained atthe refluxing temperature of isooctane for a period of 4 hours, whilethe vessel was continuously swept by a stream of purified nitrogen. 12.5milliliters of this slurry containing about 5 1O* gram atoms of titaniumand 0.5 gramof silica was then transferred, without being exposed to theatmosphere, from this reaction vessel to'a 'second 500 milliliter, threeneck, glass reaction vessel which had been previously flushed with drynitrogen 87.5 milliliters of isooctane was then charged to this secondvessel and the vessel was saturated with ethylene. Next, 0.25 millimoteof triisobutyl aluminum was added and the contents of said secondreaction vessel were continuously'and vigorously stirred, and ethylenewas. continuously swept through. the reaction vessel for about fourhours. The reaction products were analyzed and it was found that nosolid polymer of the ethylene had been produced. f Example 31 i To a2,000 milliliter, three neck, glass reaction vessel there was added 30grams of Cab-o-sil silica. Said reaction vessel was then placed in anoven heated to a temperature of about 110 C., for about twelve hours.Subsequently, the vessel was sealed without exposing said silica to theatmosphere and there was charged to said vessel 40.5 millimoles oftitanium tetrachloride and 1200 milliliters of isooctane. The vessel wasthen continuously agitated and heated to, and maintained at therefluxing temperature of isooctane for a period of 5 hours, while theHCl produced was continuously removed by sweeping the reactor vesselwith purified nitrogen. 0.45 gram of this silica containing about 6 10-gram atoms of titanium chemically bound to the surface thereof, andsuspended in about 18 milliliters of isooctane was then transferred fromthis reaction vessel to a 1000 milliliter stirred autoclave which hadbeen previously flushed with dry nitrogen. 40 milliliters of isooctane,202 grams of liquid propylene, 8 grams of liquid butadiene and 11.9grams of ethylene were then charged to the autoclave. Next, 1 millimoleof triisobutyl aluminum was added and the contents of the autoclave werecontinuously and vigorously stirred, and ethylene was continuously fedto the reaction vessel through a pressure regulator for about 2 hoursduring which time the temperature of the autoclave was maintained atabout 50 C. The reaction products were analyzed and it was found that 53grams of a rubbery terpolymer of propylene, ethylene and butadiene hadbeen produced.

Example 32 To a 1,000 milliliter, three neck, glass reaction vesselthere was added 10 grams of Cab-o-sil silica. Said reaction vessel wasthen placed in an oven heated to a temperature of about 110 C., forabout twelve hours. Subsequently, the vessel was sealed without exposingsaid silica to the atmosphere and there were charged to said vessel 5.6millimoles of tungsten hexachloride and 530 milliliters of benzene. Thevessel was then heated to and maintained at C. for a period of 5 hours,while the HCl produced was continuouslyremoved by sweeping the reactionvessel with purified nitrogen. Subsequently, the extent of the reactionbetween the silica and the tungsten hexachloride was determined bymeasuring the quantity of HCl removed from the vessel and by testing thebenzene solvent for the absence therein of tungsten chlorides and thesaid silica was found to have 5.6 10 gram atoms of tungsten bound to thesurface thereof. 1.94 grams of this treated silica, having 1.1 10" gramatoms of tungsten bound to the surface thereof, and sus pended in about104 milliliters of benzene was then transferred from this reactionvessel to a 425 milliliter, stainless steel bomb which had beenpreviously flushed with dry nitrogen. Then, the bombwas charged withethylene to a pressure of 300 p.s.i.g. Next, 0.9 millimole oftriisobutyl aluminum was added and the bomb was heated to a temperatureof about 50 C. and was occasionally and mildly stirred for about 82hours. The reaction products were analyzed and it was found that 8.9grams of polyethylene had been produced.

Example 33 To a 1,000 milliliter, three neck, glass reaction vesselthere was added 10 grams of Cab-o-sil silica. Said reaction vessel wasthen placed in an oven heated to a temperature of about C. for abouttwelve hours. Subs'equently, the vessel was sealed without exposing saidsilica to the atmosphere and there was charged to said vessel 10millimoles of chromium trichloride complexed with approximately 30millimoles of tetrahydrofuran and 500 milliliteres of benzene. Thechromium trichloride was complexed with tetrahydrofuran' (THF) in orderto increase solubility of the chromium trichloride in benzene. Thevessel was then heated to and maintained at 80 C. for a period of 5.5hours, while the HCl produced was continuously removed by sweeping thereaction vessel with purified nitrogen. Subsequently, the extent of, the

reaction between the silica and the chromium trichloride was determinedby measuring the quantity of HCl removed from the vessel and by testingthe benzene solvent for the absence therein of chromium chlorides andthe said silica was found to have 10 10 gram atoms of chromium bound tothe surface thereof. 0.59 gram of this treated silica having about 5 X-gram atoms of chromium bound to the surface thereof, and suspended inabout 29 milliliters of benzene was then transferred from this reactionvessel to a 500 milliliter, three neck, glass reaction vessel which hadbeen previously flushed with dry nitrogen. 71 milliliters of isooctanewas then charged to this second vessel and the vessel was saturated withethylene. Next, 1 millimole of aluminum triisobutyl was added and thecontents of the vessel were heated to a temperature of about 60 C. andwere continuously and vigorously stirred and ethylene was continuouslyswept through the reaction vessel at a rate somewhat faster than itsconsumption for about 3.2 hours. it was found that 14 grams ofpolyethylene had been produced.

Example 34 To a 1,000 milliliter, three neck, glass reaction vesselthere is added 10 grams of magnesia, having an average particle diameterof about 1 micron and a hydroxyl group content on the surface thereofabout 0.5 milliequivalent per gram. Said reaction vessel is then placedin an oven heated to a temperature of about 110 C., for about twelvehours. Subsequently, the vessel is sealed without exposing said magnesiato the atmosphere and there is charged to said vessel 3 millimoles ofmolybdenum trichloride and 500 milliliters of benzene. The vessel isthen heated to and maintained at the refluxing temperature of benzenefor a period of 4 hours, while the HCl produced is continuously removedby sweeping the reaction vessel with purified nitrogen. Subsequently,the extent of the reaction between the magnesia and the molybdenumtrichloride is determined by measuring the quantity of HCl removed fromthe vessel and by testing the benzene for the absence therein ofmolybdenum trichloride and the said magnesia is found to have 3x10 gramatoms of molybdenum bound to the surface thereof. 1 gram of this treatedmagnesia containing about 3 10- gram atoms of molybdenum bound to thesurface there of, and suspended in about 100 milliliters of benzene isthen transferred from this reaction vessel to a 425 milliliter,stainless steel bomb which has been previously flushed wtih dry nitrogenand said bomb is then saturated with isobutylene. Next, 1 millimole oflithium butyl, grams of liquid butene-l and 10 grams of liquid isopreneare added and the contents of the bomb are continuously and vigorouslystirred, for about 10 hours. The reaction products are analyzed and itis found that 10 grams of a copolymer of butene-l and isoprene have beenproduced.

In one embodiment of the present invention, hydrogen is introduced intothe reaction zone during the polymerization reaction. The introductionof hydrogen is not essential but generally substantially improves theyield and produces a larger proportion of xylene-soluble product. Also,the molecular weight of the product can generally be varied by varyingthe quantity of hydrogen utilized. Although the exact function of thehydrogen is not completely understood, and there is therefore, nointention to be bound by this explanation, it is believed that thehydrogen serves as chain transfer agent, thereby promoting thedissociation of polymer chains from the polymerization sites of thecatalysts and aiding the initiation and formation of additional polymerchains on said catalyst sites.

Non-limiting illustrative examples follow:

Example To a 2,000 milliliter, three neck, glass reaction vessel therewas added 20 grams of Cab-o-sil silica. Said reaction vessel was thenplaced in a vacuum drying oven heated to a temperature of about 110 C.,for about twelve hours. Subsequently, the vessel was sealed withoutexposing said silica to the atmosphere and there were charged to saidvessel 19.6 millimoles of titanium tetrachloride and 1000 milliliters ofisooctane. The vessel was then heated to, and maintained at, therefluxing temperature of isooctane for a period of 4 hours, while theHCl produced was continuously removed by sweeping the reactor vesselwith purified nitrogen. Subsequently, the extent of the reaction betweenthe titanium tetrachloride and the HCl was determined by measuring thequantity of HCl removed from the vessel by the nitrogen stream, and bydetermining the titanium tetrachloride content of the supernatantliquid, and the said silica was found to.

have 19.6 10" grarn atoms of titanium chemically bound to the surfacethereof. 1 gram of this silica containing about 1 10 gram atoms oftitanium chemically bound to the surface thereof, and suspended in about51 milliliters of isooctane was then transferred, without exposure tothe atmosphere, from this reaction vessel to a 1,000 milliliter, stirredautoclave, which had been previously flushed with dry nitrogen. 2.60milliliters of isooctane, and sufiicient hydrogen and ethylene toestablish a partial pressure therein of 300 lbs./ in. and lbs.'/ in.respectively were then charged to the autoclave. Next, 1 millimoie oftriisobutyl aluminum was added, the autoclave was heated to 60 C. andthe run was continued for about 0.5 hour during which time sufficienthydrogen and ethylene were supplied to the autoclave to maintain thepartial pressures therein as set forth above. The reaction products wereanalyzed and it was found that 128.9 grams of polyethylene, having aweight average molecular weight of about 100,000 and a melt index ofabout 1.35 had been produced.

Polymerization runs essentially similar to the above run except thatthey were conducted in the absence of hydrogen, produced polymer havinga weight average molecular weight in excess of 1,000,000 and a meltindex of about zero.

Example 36 To a 1,000 milliliter, three neck, glass reaction vesselthere was added 20 grams of Cab-o-sil silica. Said reaction vessel wasthen placed in a vacuum drying oven heated to a temperature of about C.,for about twelve hours. Subsequently, the vessel was sealed withoutexposing said silica to the atmosphere and there were charged to saidvessel 28 millimoles of titanium tetrachloride and 600 milliliters ofisooctane. The vessel was then heated to, and maintained at, therefluxing temperature of isooctane for a period of 4 hours, while theHCl produced was continuously removed by sweeping the reactor vesselwith purified nitrogen. Subsequently, the extent of the reaction betweenthe titanium tetrachloride and the silica was determined by measuringthe quantity of HCl removed from the vessel by the nitrogen stream, andby determining the titanium tetrachloride content of the supernatantliquid, and the said silica was found to have 2f 10- gram atoms oftitanium on the surface thereof. 0.8 gram of this silica containingabout 1.1 10- gram atoms of titanium bound to the surface thereof, andsuspended in about 26 milliliters of isooctane was then transferred fromthis reaction vessel without exposure to the atmosphere to a 425milliliter stainless steel bomb which had been previously flushed withdry nitrogen and which contained 1 atmosphere of hydrogen. grams ofliquid propylene was then charged to the bomb. Next, 2 millimoles oftriisobutyl aluminum was added, and the contents of the bomb were thencontinuously and vigorously stirred, in a 50 C. water bath for about 17hours. The reaction products were analyzed and it was found that 60grams of polypropylene had been produced.

It is pointed out that by controlling (a) the number of hydroxyl groupspresent on the surface of the inorganic solid, (b) the proportion oftransition metal halide which reacts with the inorganic solid, and (c)the temperature within the limits aforementioned, we can produce theinorganic solid catalyst components of the present inven tion havingchemically linked directly to the surface of the inorganic solid,halogenated atoms of a metal chosen from the group consisting of groupsIVa, Va and VIa, in which the resulting surface structures arerelatively uniform in that the predominant proportion 'of saidhalogenated metal atoms each has the same number of halogen atomsattached thereto. Such catalyst components are very useful because suchcatalyst components when used in conjunction with suitableorganometallic compounds to polymerize the monomers of the presentinvention are characterized by relatively. high specificity in that theytend to produce unusually homogeneous polyemers, that is polymers havingexceptionally high crystallinity, narrow range of molecular weight, etc.

The polymers produced by the process of this invention can be subjectedto such aftertreatment as may be desired to fit them for particular usesor to impart desired properties. Thus, the polymers can be extruded,mechanically milled, filmed or cast, or converted to sponges or latices.Also, antioxidants, stabilizers, fillers such as carbon black andsilicas, extenders, plasticizers, pigments, insecticides,

fungicides, etc., can be incorporated into the polyolefins.

Also, the polymers produced by the process of the present invention,especially the polymers having high specific viscosities can be blendedwith the lower molecular weight polyethylenes to impart stiffness orother desired properties thereto. The solid resinous products producedby the process of the present invention can, likewise, be blended in anydesired proportions with hydrocarbon oils, waxes, high bolecular weightpolybutylenes, and with other organic materials. Small proportionsbetween about 0.01 and about 1 percent of the various polymers producedby the process of the present invention can be dissolved or dispersed inhydrocarbon lubricating oils to increase VI. and to decrease oilconsumption when the compounded oils are employed in motors. Thepolymerization products having molecular weights of 50,000 or more, canbe employed in small proportions to substantially increase the viscosityof fluent liquid hydrocarbon oils and as gelling agents for such oils.

The polymers produced by the present process can also be subjected tochemical modifying treatments, such as halogenation, halogenationfollowed by dehalogenation, sulfohalogenation by treatment with sulfurylchloride or mixtures of chlorine and sulfur dioxide, sulfonation, andother reactions to which hydrocarbons may be subjected. The polymers ofour invention can also be crosslinked to effect increases in softeningtemperature, etc.

Obviously many changes may be made in the above described examples andprocedure without departing from the scope of the invention. Forexample, although only transition metal chlorides, bromides, and iodideswere mentioned in the above examples, transition metal fluorides arealso suitable for the purposes of the present invention. For example,titanium tetrafluoride is entirely suitable.

Also, pyrogenically coformed, or coprecipitated metal oxides, or metaloxides coformed with, or mixed with, other compounds are suitable forthe purposes of the present invention. It is pointed out that it isintended and it should be understood that for the purposes of thepresent specification and the claims appended thereto, the term, metaloxide, includes silica.

Accordingly, it is intended that the above disclosure be regarded asillustrative and as in no Way limiting the scope of the invention.

What we claim is:

1. A proccess for polymerizing a substance chosen from the groupconsisting of a mono-olefin, mixtures of mono-olefins, a di-olefin,mixtures of di-olefins, and mixtures thereof which comprises contactingsaid substance at temperatures between about -25 C. and about 250 C.with a catalyst comprising (a) a finely-divided inorganic solid havingan average particle diameter of less than about 0.1 micron and carryingin chemical 'ro xg V wherein T is a metal chosen from the groupconsisting of the metals of GroupsIVa, Va and VIa; O is oxygen; a is anumber from to 2; each X is any halogen; b is a number from 1 to 5; andwhere said structures'are chemically linked directly from T to at leastone oxygen atom in the surface of said solid, and (b) a compoundconforming to the general formula 1 'MM X R wherein M is chosen from thegroup consisting of the metals of Groups I, II and IH; M' is ametalofGroup I; v is a number'fro'm 0 to 1; each X is any halogen; n is anumber from 0 to 3; each Ris chosen from the group consisting of anymonovalant hydrocarbon radi cal and hydrogen; and y is a number from 1to 4.

2. The process of claim 1 wherein the substance to be polymerized isana-mono-olefin. V

3. The process of claim 1 wherein the substance to be polymerized isethylene.

4. The process of claim 1 wherein the be polymerized is propylene.

' 5. The process of claim 1 wherein the substance to be polymerized isbu ten'e-l.

6. The process of claim 1 wherein the substance to be polymerized is adi-olefin having -a double bond in the alpha position. Y r r 7. Theprocess of claim 1 wherein said finely-divided solid is a metal oxide.

8. The process of claim 1 wherein said finely-divided solid is titania.

9. The process of claim 1 wherein said finely-divided solid is silica.

10. The process of claim 1 wherein said finely-divided solid is alumina.

11. The process of claim 1 wherein each X in the formula substance to Tis a metal of Group Na.

13. The process of claim 1 wherein in the formula T is titanium, a is 0,each X is chlorine, and b is 3.

14. The process of claim 1 wherein in the formula TO X T is zirconium, ais 0, and each X is chlorine.

15. The process of claim 1 wherein in the formula T is a metal of GroupVa.

16. The process of claim 1 wherein in the formula "ro x T is vanadium.

17. The process of claim 1 wherein in the formula TO X T is a metal ofGroup VIa.

18. The process of claim 1 wherein in the formula TO X T is chromium.

19. The process of claim 1 wherein in the formula TO,,X,. ais0andbis4.

2? 20. The process of claim 1 wherein in the formula TO X aisandbis2.

21. The process of claim 1 wherein in the formula M is aluminum, v is 0,and each R is any alkyl group.

22. The process of claim 1 wherein in said general formula MM X R M isaluminum, v is 1, n is 0, and each R is any alkyl group.

23. A process for polymerizing a substance chosen from the groupconsisting of a mono-olefin, mixtures of mono-olefins, a di-olefin,mixtures of di-olefins and mixtures thereof which comprises (a) forminga cocatalyst by reacting while eliminating the hydrogen halide producedat temperatures of from about 0 C. to about 105 C. for periods rangingat a minimum from about hours to about 1 minute, the higher thetemperature used, the shorter being said minimum time required, hydroxylgroups on the surface of an inorganic solid which has an averageparticle diameter of less than about 0.1 micron and at least about 1 1O-equivalents per gram of hydroxyl groups on the surface thereof and whichis substantially free of free and physically bound water, with acompound conforming to the formula:

TO X

wherein T is a metal chosen from the group consisting of the metals ofGroups IVa, Va and VIa; O is oxygen;

a is a number from 0 to 2; each X is any halogen; and b is a number from1 to 6; (b) combining said cocatalyst with a compound conforming to thegeneral formula wherein M is chosen from the group consisting of themetals of Groups I, II and III; M is a metal of Group I; v is a numberfrom 0 to 1; each X is any halogen; n is a number from 0 to 3; each R ischosen from the group consisting of any monovalent hydrocarbon radicaland hydrogen; and y is a number from 1 to 4; and (c) contacting saidsubstance with the resulting catalyst at temperatures between about C.and about 250 C.

24. The process of claim 23 wherein said compound conforming to theformula ro x is titanium tetrachloride.

25. The process of claim 23 wherein the reaction of part (a) to formsaid cocatalyst is accomplished in a liquid hydrocarbon medium.

References Cited in the file of this patent UNITED STATES PATENTS2,924,628 Donaldson Feb. 9, 1960 2,938,000 Wanless et al. May 24, 19602,981,725 Luft et al. Apr. 25, 1961 2,989,516 Schneider June 20, 19613,054,754 Lasky Sept. 18, 1962 FOREIGN PATENTS 592,111 Italy July 28,1959 823,024 Great Britain Nov. 4, 1959

1. A PROCESS FOR POLYMERIZING A SUBSTANCE CHOSEN FROM THE GROUPCONSISTING OF A MONO-OLEFIN, MIXTURES OF MONO-OLEFINS, A DI-OLEFINMIXTURES OF DI-OLIFINS, AND MIXTURES THEREOF WHICH COMPRISES CONTACTINGSAID SUBSTANCE AT A TEMPERATURES BETWEEN ABOUT -25*C. AND ABOUT 250*C.WITH A CATALYST COMPRISING (A) A FINELY-DIVIDED INORGANIC SOLID HAVINGAN AVERAGE PARTICLE DIAMETER OF LESS THAN ABOUT 0.1 MICRON AND CARRYINGIN CHEMICAL COMBINATION ON THE SURFACE THEREOF AT LEAST ABOUT 1X10**-4EQUIVALENTS PER GRAM OF STRUCTURES CONFORMING TO THE FORMULA